CN107698429B - A kind of method of functionalized ion liquid catalytic synthesis of bisphenol fluorene - Google Patents
A kind of method of functionalized ion liquid catalytic synthesis of bisphenol fluorene Download PDFInfo
- Publication number
- CN107698429B CN107698429B CN201710876619.2A CN201710876619A CN107698429B CN 107698429 B CN107698429 B CN 107698429B CN 201710876619 A CN201710876619 A CN 201710876619A CN 107698429 B CN107698429 B CN 107698429B
- Authority
- CN
- China
- Prior art keywords
- phenol
- ionic liquid
- bisphenol fluorene
- cation
- catalytic synthesis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 31
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 13
- 239000007788 liquid Substances 0.000 title description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002608 ionic liquid Substances 0.000 claims abstract description 25
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000006482 condensation reaction Methods 0.000 claims abstract description 13
- -1 benzothiazolyl cation Chemical class 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000012071 phase Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 12
- 239000007790 solid phase Substances 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003426 co-catalyst Substances 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract description 3
- 238000001953 recrystallisation Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000003915 air pollution Methods 0.000 abstract 1
- 231100000572 poisoning Toxicity 0.000 abstract 1
- 230000000607 poisoning effect Effects 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000011831 acidic ionic liquid Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- LNNIPFBETXOKIA-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-9h-fluoren-2-yl]phenol Chemical class C1=CC(O)=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=C(O)C=C1 LNNIPFBETXOKIA-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of methods of catalytic synthesis of bisphenol fluorene, using phenol and 9-Fluorenone as raw material, using proton acidic functionalized ionic liquid as catalyst, carry out condensation reaction；The proton acidic functionalized ionic liquid is made of anion and cation；The cation is benzothiazolyl cation or benzimidazolyl cation；The anion is HSO4 ‑、H2PO4 ‑、BF4 ‑、Tos‑.The method of the present invention is using phenol and Fluorenone as raw material, and under proton acidic functionalized ionic liquid catalytic action, easy to operate, the reaction time is short, small to equipment corrosion, and reaction conversion ratio reaches 100%, and product purity is very high after recrystallization.Entire reaction process does not need co-catalyst, is thus avoided that and causes worker's poisoning and air pollution in production process.In addition to this, proton acidic functionalized ionic liquid and phenol are by being evaporated under reduced pressure equal recoverable, and greatly reduce the pollution of phenol and the concentrated sulfuric acid to environment.
Description
Technical field
The present invention relates to bisphenol fluorene preparation fields, and in particular to a kind of functionalized ion liquid catalytic synthesis of bisphenol fluorene
Method.
Background technique
Bis- (4- hydroxyphenyl) fluorenes of bisphenol fluorene i.e. 9,9-, molecular formula C25H18O2, molecular weight 350.4,222 DEG C of fusing point~
224 DEG C, white powder substance dissolves in the organic solvents such as acetonitrile, toluene, methanol, isopropanol, methylene chloride.
It is raw material in the presence of acidic through Cardo prepared by condensation reaction that bisphenol fluorene, which is using Fluorenone and phenol,
The bisphenol compound of ring skeleton structure.In modern polymerization process industry, bis-phenol fluorene compound and its substitutive derivative conduct
Important monomer is largely used to condensation reaction, particularly for prepare high temperature resistant, good luster performance, high flame resistance
The polycondensation products such as polycarbonate, polyurethane, polyethers.The polycondensation products as made from bisphenol fluorene can be used as heat proof material, photosensitive material
Material, electrical conductor material and high-temperature resistant coating etc., are widely used in the fields such as aircraft, space flight and aviation, automobile, military affairs, electronics
It is widely used.
Different according to used catalyst, the method for the bisphenol fluorene synthesizing of existing patent literature report is as follows at present
It is shown:
(1) synthetic method reported in U.S.Pat.No.4675458: being starting material and phenol in dense sulphur using 9-Fluorenone
Under acid catalysed conditions, bisphenol fluorene synthesizing, yield is about 85%, but a large amount of phenol wastewater are generated in this method washing process, to ring
Border causes seriously to pollute, and processing is difficult.Therefore, which is eliminated substantially.
(2) synthetic method reported in U.S.Pat.No.5149886: being starting material and phenol in chlorination using 9-Fluorenone
Hydrogen is as bisphenol fluorene synthesizing under catalytic condition, yield 85%, but hydrochloride aqueous solution corrosivity is strong, to damage of facilities
Greatly, and production operation is cumbersome, and security risk is big.
(3) synthetic method reported in Chinese invention patent application prospectus CN1617845: in 9-Fluorenone, benzene
Phenol, strong-acid ion exchange resin and mercaptopropionic acid catalytic synthesis of bisphenol fluorene, catalyst is recyclable, it is small to corrode to equipment；But it is anti-
Long between seasonable, catalyst is at high cost.
(4) research [J] Chemical Engineer of Gao Qingping, Wang Wenzheng Catalyzed by Phosphotungstic Acid bisphenol fluorene synthesizing, 2009,
23 (6): the synthetic method reported in 12-13: heteropoly acid bisphenol fluorene synthesizing is applied, bisphenol fluorene yield is 65.3%, although can
It realizes catalyst recycling but catalyst is at high cost, the reaction time is long, and needs co-catalyst.
(5) research [D] that Shen Maochang .Bronsted presence of acidic ionic liquid catalyst 9-Fluorenone is reacted with phenol condensation, Dalian
Polytechnics, 2015, the synthetic method of middle report: using 9-Fluorenone and phenol as raw material, urged in functionalization acidic ionic liquid plus help
Bisphenol fluorene synthesizing under the conditions of agent, this method conversion ratio can reach 100% and catalyst is easy recycling and reusing, but whole process
Need to consume co-catalyst mercaptan carboxylic acid, mercaptan carboxylic acid is with foul smell and has severe toxicity, and price is relatively high.
Summary of the invention
Insufficient in the prior art in order to overcome, the present invention provides a kind of functionalized ion liquid catalytic synthesis of bisphenol fluorene
Method, this method reaction time is short, and reaction conversion ratio is up to 100%, and solid crude product yield is up to 95%, does not need to help and urge
Agent, it is small to equipment corrosion, and catalyst and the equal recoverable of phenol, it is low in the pollution of the environment, production cost is reduced, is suitble to
The preparation method of industrialized production.
The technical scheme adopted by the invention is that a kind of method of catalytic synthesis of bisphenol fluorene, is original with phenol and 9-Fluorenone
Material carries out condensation reaction using proton acidic functionalized ionic liquid as catalyst；
The proton acidic functionalized ionic liquid is made of anion and cation；
The cation is benzothiazolyl cation [(CH2)3SO3HBth]+Or benzimidazolyl cation [(CH2)3SO3HBim]+；
Its structural formula are as follows:
The anion is HSO4 -、H2PO4 -、BF4 -、Tos-。
Cation is preferably benzothiazolyl.
Most preferably, the proton acidic functionalized ionic liquid is [(CH2)3SO3HBth][HSO4]。
As a preferred technical solution, in the condensation reaction, the molar ratio of phenol and 9-Fluorenone is 1:4~1:10,9-
The molar ratio of Fluorenone and proton acidic functionalized ionic liquid is 1:0.1~1:0.45.
The condition of the condensation reaction is 60~150 DEG C of temperature as a preferred technical solution, and the reaction time 2~10 is small
When.
It is highly preferred that 90~110 DEG C of reaction temperature, the reaction time 4~6 hours.
In condensation reaction, phenol is not only used as reactant, but also as reaction dissolvent.
Preferred 5:1~the 8:1 of the molar ratio of the phenol and 9-Fluorenone, 9-Fluorenone and proton acidic functionalized ionic liquid
Preferred 1:0.3~the 1:0.4 of molar ratio, the ratio can be such that 9-Fluorenone 100% converts.
The method also includes being filtered and obtained using washing, decompression after condensation reaction as a preferred technical solution,
After solid product, then methylene chloride is used to recrystallize the solid product.
The recrystallization solvent can also be any one of ethyl alcohol, isopropanol, methanol, methylene chloride, acetone,
The present invention is preferably methylene chloride.
Decompression filters to obtain solid particulate matter and filtrate, and solid particulate matter is dry to get the crude product for arriving bisphenol fluorene, Gu
Body yield is up to 95%.Bisphenol fluorene, product yield about 89% are recrystallized to obtain, purity is greater than 99%.
The washing is the water washing for first using 5~25 DEG C as a preferred technical solution, obtains water phase A and solid phase A；Again
The solid phase A is washed using 70~90 DEG C of water, obtains aqueous phase B and the solid product.The mesh of 5~25 DEG C of water washings
Be recycle proton acidic functionalized ionic liquid, the purpose of 70~90 DEG C of water washings be recycle phenol, so as to Bronsted acid function
Further recycling for ionic liquid and phenol can be changed.
The method also includes being recycled after re-crystallization as a preferred technical solution, comprising the following steps: subtracts
Pressure distills the water phase A and recycles proton acidic functionalized ionic liquid, is evaporated under reduced pressure the aqueous phase B recycling phenol.
It is highly preferred that at room temperature, the mixed liquor that condensation reaction obtains is poured into beaker while hot, it is added in beaker suitable
5~25 DEG C of water washings, stratification are measured, upper layer is water phase, and lower layer is oily sticky solid.It separates water phase and oily is sticky solid
Body phase, acidic functionalized ionic liquid containing proton and a small amount of phenol in water phase are to be processed；In oily sticky solid be added 70~
90 DEG C of hot water, are stirred, stratification with glass bar, and upper layer is water phase, and lower layer is still oily sticky solid, separation water phase and oil
Shape sticky solid phase repeats aforesaid operations, until plus stir after removing 90 DEG C of hot water, solid phase is no longer sticky, and solid becomes
It is granular, stop aforesaid operations.70~90 DEG C of water phases for depressurizing the filtrate filtered and washing oily sticky solid merge, through depressurizing
Water is distilled off and collects to obtain phenol, phenol recovery rate is up to 80%.
Detailed description of the invention
Fig. 1 is the liquid chromatogram of 1 distillate sample of embodiment；
Fig. 2 is the influence that Pyrogentisinic Acid and Fluorenone condensation reaction is recycled in 1 ionic liquid of embodiment.
Specific embodiment
Embodiment 1
Ionic liquid [(CH2)3SO3HBth][HSO4] preparation in preparation method, it is specific the preparation method is as follows: will
The benzothiazole of 0.2mol is added in the three-necked flask of 100mL, and 30mL dehydrated alcohol is added in three-necked flask, constantly stirs
It mixes down, the 1,3-propane sultone of equimolar amounts is added dropwise into reaction flask with constant pressure funnel；After completion of dropwise addition, it is warming up to
90 DEG C of reaction 4h.After reaction, it is washed respectively three times with acetone and ether 20mL, vacuum at filtered filter cake and 80 DEG C
Dry 6h, obtains intermediate amphoteric ion.The amphoteric ion intermediary of 5g is added in the round-bottomed flask of 50mL, adds the water of 20mL
For solvent, the sulphur of equimolar amounts is slowly added dropwise, pays attention to stirring during being added dropwise.After completion of dropwise addition, 80 DEG C of heating water bath, instead
6h is answered, after reaction, removes water with revolving first, then washed three times with 15mL ether.Obtained crude product vacuum at 80 DEG C is dry
Dry 6h obtains ionic liquid [(CH2)3SO3HBth][HSO4], nuclear magnetic data is as follows:1H NMR(400MHz,D2O, TMS): δ
(ppm):8.98(s,1H),8.18-8.06(m,2H),7.82-7.76(t,1H),7.74-7.25(t,1H), 4.81(t,2H),
2.93(t,2H),2.42-2.27(m,2H)。
The preparation of bisphenol fluorene: accurately weighing a certain amount of Fluorenone, is added into the three-necked flask of 50mL, is then added suitable
The phenol of amount, ionic liquid [(CH2)3SO3HBth][HSO4], at one 90 DEG C, heating, reflux 6h uses glass after reaction
Glass stick dips suitable reaction solution and is dissolved in CH3In OH, analyzed it with liquid chromatogram.Reaction solution is poured into beaker while hot
In, appropriate 20 DEG C of water is added in beaker and is washed, stratification, upper layer is water phase, and lower layer is oily sticky solid.Point
From water phase and oily sticky solid phase, ionic-liquid catalyst and a small amount of phenol are contained in water phase, it is to be processed；It is sticky solid in oily
90 DEG C of hot water are added in body, are stirred with glass bar, stratification, upper layer is water phase, and lower layer is still oily sticky solid, separation
Water phase and oily sticky solid phase repeat aforesaid operations, until plus stir after removing 90 DEG C of hot water, solid phase is no longer sticky, solid
Become graininess, stops aforesaid operations.Decompression filters, and obtains solid particulate matter and filtrate, and solid particulate matter drying is arrived
The crude product of bisphenol fluorene, solid yields 94%.Bisphenol fluorene is recrystallized to obtain, bisphenol fluorene yield 89%, product purity is greater than
99%.Nuclear magnetic data is as follows:1H NMR (400MHz, Chloroform-d) δ 7.75 (dt, J=7.4,1.0Hz, 2H), 7.39-
7.31(m,4H),7.30–7.23(m,2H),7.09–7.03 (m,4H),6.70–6.64(m,4H).13C NMR(101MHz,
Chloroform-d)δ154.19, 151.71,139.93,138.30,129.37,127.68,127.34,125.98,
120.13,114.98.The water phase of the filtrate that decompression is filtered and 90 DEG C of washing oily sticky solids merges, and removes through vacuum distillation
Water is gone to collect to obtain phenol, phenol recovery rate is up to 80%, by 30 DEG C of water phase vacuum distillation recycling ionic liquid, so as to ion
Liquid and phenol further recycle.By efficient liquid phase chromatographic analysis, as shown in Figure 1, reaction conversion ratio is 100%.
The circulation experiment of catalyst ion liquid: accurately weighing a certain amount of Fluorenone, is added to the three-necked flask of 50mL
In, suitable phenol is then added, ionic liquid, at a certain temperature, heating flow back a few hours, after reaction, return
Receive ionic liquid；Examine [(CH2)3SO3HBth][HSO4] be recycled effect.Specific experiment operation is as follows: reacting
After, quantitative deionized water is added into reaction flask, stirs, static layering, supernatant liquid is transferred to 50mL single neck round bottom
In flask, revolving water removal is washed 3 times with ether, is reused after being dried in vacuo 2-3h at 100 DEG C, recycles five catalysis
Activity is without being decreased obviously, as shown in Figure 2.
Above embodiments are preferable implementation process of the invention, not do more limitation to the present invention.All foundations
Simple modification or equivalent variation and modification are made to technological essence of the invention, still belong to the scope of protection of the invention.
Claims (6)
1. a kind of method of catalytic synthesis of bisphenol fluorene, which is characterized in that using phenol and 9-Fluorenone as raw material, with proton acid functionalization
Ionic liquid is catalyst, carries out condensation reaction；
The proton acidic functionalized ionic liquid is made of anion and cation；
The cation is benzothiazolyl cation or benzimidazolyl cation；
The anion is HSO4 -、BF4 -、OTs-。
2. the method for catalytic synthesis of bisphenol fluorene according to claim 1, which is characterized in that in the condensation reaction, phenol
Be 1:4~1:10 with the molar ratio of 9-Fluorenone, the molar ratio of 9-Fluorenone and proton acidic functionalized ionic liquid be 1:0.1~
0.45。
3. the method for catalytic synthesis of bisphenol fluorene according to claim 1, which is characterized in that the condition of the condensation reaction is
60~150 DEG C of temperature, the reaction time 2~10 hours.
4. the method for catalytic synthesis of bisphenol fluorene according to claim 1, which is characterized in that the method also includes being condensed
After reaction, filtered using washing, decompression after obtaining solid product, then the solid product is tied again using methylene chloride
It is brilliant.
5. the method for catalytic synthesis of bisphenol fluorene according to claim 4, which is characterized in that the washing be first using 5~
25 DEG C of water washing obtains water phase A and solid phase A；The solid phase A is washed using 70~90 DEG C of water again, obtains aqueous phase B and institute
State solid product.
6. the method for catalytic synthesis of bisphenol fluorene according to claim 4 again, which is characterized in that the method also includes tying
It is recycled after crystalline substance, comprising the following steps: be evaporated under reduced pressure the water phase A recycling ionic liquid, be evaporated under reduced pressure the phase B recycling benzene
Phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710876619.2A CN107698429B (en) | 2017-09-25 | 2017-09-25 | A kind of method of functionalized ion liquid catalytic synthesis of bisphenol fluorene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710876619.2A CN107698429B (en) | 2017-09-25 | 2017-09-25 | A kind of method of functionalized ion liquid catalytic synthesis of bisphenol fluorene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107698429A CN107698429A (en) | 2018-02-16 |
| CN107698429B true CN107698429B (en) | 2019-11-26 |
Family
ID=61174868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710876619.2A Active CN107698429B (en) | 2017-09-25 | 2017-09-25 | A kind of method of functionalized ion liquid catalytic synthesis of bisphenol fluorene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107698429B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250049B (en) * | 2018-03-25 | 2021-04-27 | 明天塑料(上海)有限公司 | Synthesis method of bisphenol fluorene |
| CN108570019B (en) * | 2018-05-31 | 2021-02-26 | 大连理工大学 | Acidic ionic liquid and catalytic application thereof |
| CN116444345A (en) * | 2023-04-25 | 2023-07-18 | 郑州中科新兴产业技术研究院 | Method for preparing fluorenyl dihydric alcohol by utilizing sulfonic acid type ionic liquid catalysis |
| CN116444346A (en) * | 2023-04-25 | 2023-07-18 | 郑州中科新兴产业技术研究院 | Method for synthesizing bisphenol compound by catalysis of supported ionic liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986509A (en) * | 2006-12-20 | 2007-06-27 | 哈尔滨工程大学 | Bisphenol fluorene synthesizing process catalyzed with solid supported heteropolyacid |
| CN101003466A (en) * | 2007-01-19 | 2007-07-25 | 哈尔滨工程大学 | Method for synthesizing bisphenol fluorine by catalysis of highly acidic cation exchange resin |
| CN105152867A (en) * | 2015-05-03 | 2015-12-16 | 上虞日月星科技化学有限公司 | Bisphenol fluorene compound and preparation method thereof |
| CN105693475A (en) * | 2016-03-15 | 2016-06-22 | 辽宁大学 | Technology method for utilizing solid acid H2SO4-SiO2 for catalyzing and preparing bisphenol |
-
2017
- 2017-09-25 CN CN201710876619.2A patent/CN107698429B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986509A (en) * | 2006-12-20 | 2007-06-27 | 哈尔滨工程大学 | Bisphenol fluorene synthesizing process catalyzed with solid supported heteropolyacid |
| CN101003466A (en) * | 2007-01-19 | 2007-07-25 | 哈尔滨工程大学 | Method for synthesizing bisphenol fluorine by catalysis of highly acidic cation exchange resin |
| CN105152867A (en) * | 2015-05-03 | 2015-12-16 | 上虞日月星科技化学有限公司 | Bisphenol fluorene compound and preparation method thereof |
| CN105693475A (en) * | 2016-03-15 | 2016-06-22 | 辽宁大学 | Technology method for utilizing solid acid H2SO4-SiO2 for catalyzing and preparing bisphenol |
Non-Patent Citations (2)
| Title |
|---|
| "Bronsted酸性离子液体催化9_芴酮与苯酚缩合反应的研究";申茂昌;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20170315(第3期);B014-134 * |
| "离子液体中烷基化反应和缩合反应的研究";胡燚;《中国优秀博硕士学位论文全文数据库 (博士) 工程科技Ⅰ辑》;20051215(第8期);B014-11 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107698429A (en) | 2018-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107698429B (en) | A kind of method of functionalized ion liquid catalytic synthesis of bisphenol fluorene | |
| TWI633096B (en) | Method for purification of compound or resin | |
| CN108570019B (en) | Acidic ionic liquid and catalytic application thereof | |
| CN109331873B (en) | Method for preparing diacetone acrylamide by using temperature-controlled phase-change type heteropoly acid ionic liquid catalyst | |
| CN107297222B (en) | Preparation and application method of polyion liquid solid acid catalyst | |
| CN102516128B (en) | Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis | |
| CN101773860A (en) | Carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process | |
| KR20090115735A (en) | Sulfonic acid group-containing carbonaceous material | |
| CN105777488A (en) | Method for catalytically preparing fatty alcohol | |
| CN102516139A (en) | Synthesis method of phenyl sulfide compound | |
| CN102627532A (en) | Use of copper alginate | |
| CN101003466A (en) | Method for synthesizing bisphenol fluorine by catalysis of highly acidic cation exchange resin | |
| CN111215138A (en) | catalyst, preparation method and application of catalyst in preparation of β -isophorone | |
| CN113248441A (en) | Dual-functional ionic liquid, preparation method thereof and application thereof in catalytic synthesis of bisphenol compound | |
| CN101735020A (en) | Process for the catalytic synthesis of bisphenol fluorene by using concentrated sulphuric acid | |
| CN105693475B (en) | A kind of solid acid H2SO4‑SiO2Catalysis prepares the process of bisphenol fluorene | |
| CN116444346A (en) | Method for synthesizing bisphenol compound by catalysis of supported ionic liquid | |
| CN102786436B (en) | A kind of method of synthesizing cyanoacetate | |
| CN109942436B (en) | Method for preparing N, N-dialkyl aniline compound by alkylation of alkyl p-toluenesulfonate | |
| CN108558625B (en) | Synthesis method of boron trifluoride catalyzed benzophenone compound | |
| CN101880228A (en) | Clean preparation method for butyl acetate | |
| CN108250049B (en) | Synthesis method of bisphenol fluorene | |
| CN115057841B (en) | Method for preparing 1, 2-methylenedioxybenzene | |
| CN110054554B (en) | Method for synthesizing 4-phenyl-3-butenone | |
| CN112279751B (en) | Method for synthesizing bisphenol compound by using solid acid as catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |